Lubricating composition



Patented Oct. 3i, 1939 'EES NET

PATENT ornca LUBBHGATING COMPO SH'EIUN (Jarl lF. Tirutton, East@leveland, and Albert K. Smith, Shaker Heights, 0hio,' assignoi's, bymesne assignments, to The Lnbri-Zol Development @orporation; Cleveland,Ohio, 2;, corporation of Delaware No Brag.

22 (Claims.

This invention relates as indicated to lubricating co'mpcsitionsand moreparticularly to compositions for use in connection with the lubricationof relatively moving metallic surfaces which are subjected-to or liableto be subjected to exing metallic surfaces are subjected to extremepressure, i. e., for the definition of extreme pressure lubrication andthe distinction thereof over low pressure or thick film lubrication,reference may be had to the specification of the above mentionedapplication.

It is among the objects of this invention to pro-= vide a lubricatingcomposition which may be employed to reduce the friction betweenrelatively movable metallic surfaces underpressures and other factorswhich resultin what has been above explained as thick film lubricationand a composition which' may be employed for thin film lubrication andwithout a'material increase in the coefiicient of friction between theparts over that found during thick film lubrication.

In the co-pending application of Carl F. Prutton, Serial No. 679,594,filed July 10, 1933, there is disclosed the use of halogenated organiccompounds as addition-agents to lubricating compositions such ascomprise principally mineral oil and as stated in the specification ofsuch application, the addition of the halogenated organic compounds tothe oil base impart extreme pressure characteristics to the compositionnot possessed by the 'pure'petroleum oil. I

It is a further object of this invention to provide an additionalimprovement in such lubricating compositions as disclosed in the lastabovementioned .application by the further addition theretoof certainmaterials.

Other objects of this invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, said invention,then, consists of the means hereinafter fullyv described andparticularly pointed out in the claims, the following descriptionsetting forth in detail one approved combination of ingredientsembodyingour in- Application December i, 1934, Serial No. 755,988

vention, such disclosed means constituting, however, but one Of variousforms in which the prin-. ciple of the invention may be used.

Particularly stated, this invention comprises the combined use as alubricating composition of organic halogen bearing compounds and sulphurin active form; and the combined use of both such materials as additionagents to lubricating compositions which also contain a suitable 111- wbricating oil such as mineral oil.

The suitable oil which may be used in providing one of the lubricatingcompositions contem plated by this invention may be any vegetable ormineral oil or a sulphur treated oil. For the definition of the termsulphur-treated oil reference may be had to the portion of thisspecification referring to the form in which sulphur may be present inthe oil.

- Our invention, as above explained, contemplates the use of halogenatedcompounds in such proportions as not to materially reduce the viscosityof the lubricating composition.

Since the loss of such additions by volatilization will in general beless for higher boiling materials,

' the boiling point should be at least 125 C. and

preferably above 140 C. In other words, in order that the additionagents may not be driven ofi from the ultimate composition duringelevated temperatures encountered during use they should have a vaporpressure less than atmospheric at a temperature of 125 C. and preferablyat a temperature of 140 C.

The halogenated organic compounds used are preferably of such nature asto be sufficiently stable so that they will not cause corrosion of thebearings and other metallic parts exposed to the lubricant. Thesereouirements in general are met more spec fically bv the, halogenatedorganic ring compounds as distinguished from open chain compounds. Thechlorinated species of these compounds is preferred particularly due totheir low cost and superiority of performance. The halogenated organicring compounds which have been found to produce very satisfactoryresults are as follows:

Halogen bearing derivatives of:

I Benzene such as:

(l) Halogenated benzene, e. g.,

Monchlorbenzene;

The dichlorbenzenes, notably the ortho compound; the memo:- benzenes,notably the 1, 2, 4 compound,

(2) Halogenated derivatives of benzene (b) Halogenated aminoderivatives,

Such 8.5 e, g

(a) Halogenated homologs of benchlorinated phenanthryla- Z8118, 8. g.mines chlorinated toluene chlorinated anthramines 5 chlorinated xylene(c) Halogenated h y d r o p h e n- Chlorinated y e anthrenes andhalogenated (b) Halogenated amino derivatives hydroanthracene f benzene,V Chrysene, and picene, including haloo n ted a e genation products oftheir derivatives 10 chlorinated toluidines including homologs and othersubstichlorinated xylidines tution products.

( a genated hydrobenzenes, VI Bridged ring compounds, such asderivatives of the terpenes and related dichlorhexahydrobenzenecompounds. (dichlorcyclohexane) VII Heterocyclic compounds, such ashalo- H Polyphenyls. including ph nyl, diphenyl gen bearing derivativesof pyridine, benzenes, etc., such as, quinoline, pyrrole, thiophene and(1) Chlorinated diphenyl furan.

(2) Halogenated derivatives of diphenyl,

such as, It will be noted that the above enumerated ex- (a) Halogenatedhomologs of amples of organic ring compounds which are phenyLepreferably employed are, in general, compounds chlorinated pheny1to1uenes of the aryl type, i. e., compounds containing 1; Hamgenatedamino derivatives benzenoid ring structures and also of the type in ofdipheny1e which the halogen is directly attached to an chlorinatedphenyl anilines atom which is a part of such ring structure. chlorinatedh 1 t 1 As a matter of convenience, the halogenated (c) Habgenatedhydrodiphenylsb diphenyls and substituted diphenyls, as well ashalogenated substituted benzenes where two or chlorinat d phenyl hexahymore phenyl groups are directly linked, may be drobenzene inclusivelyreferred to as halogenated polychlorinated dodecahydrodi- PhenylsphenylOf, the cha n compounds which may be em- ];[I Naphthalene such asployed, such as hexachlorethane, acetylene, tetra- 85 (1 Chlorinatednaphthalene chloride, butylene dichloride (1 2 dl-chlorbu- 2 Halogenatedderivatives f naph tane), monochlorhexane, 1-2 d1chlor hexane,

' thalene such amylene dichloride, etc. or 'any other halogen (a)Hamgenated homologs ofv naph substitution or addition products of theparaffins, tha1enes chlorinated olefines or acetylenes or derivatives ofthem, the methyl naphthalene notably less volatile and more stable arepreferred for the the alpha compound ch1o reasons above set forth.rmated propyl and isopropyl Certain halogenated commercial productssubstitution produ cts f which are mlxtures of such compounds are alsonaphthalene adapted for this use, such as: chlorinated wax, bHalozenated amino derivatives chlorinated kerosene, chlorinated motoroil, etc. of naphthalene, e m It has been found that the effectivenessof ated naphthylamines halogenated organic compounds in increas ng the(c) Hamgenated n y d r o n a film strength of lubricating compositionsis augthalenes, chlorinated mented by the presence of oxygen. Suchoxygen cahydronaphthalene may be present in the form of a separateorganic 1v phenanthrene and anthracene such compound or preferably inthe same compound as Chlorinated phenathrene, chlorim the halogen. Apreferred type of composition as ated anthracene contemplated by thisinvention is therefore one in 2 Hamgenated derivatives of phenam whichthe halogen is present in the form of a Irene and anthracene such as:halogenated oxygen-bearmg organic ring com- (a) Halogenated homologs, e.g. pound chlorinated '1- t 1 phen The sulphur present in the compositionmay anthrene occur as elemental sulphur in solution or in a hl t3-methy1 Phenstable form of colloidal suspension or as sulphurcoanthrene treated oils.

chlorinated 9,10 dimethyl By the term sulphur-treated oil as employedphenanthrene in this description is meant any suitable oil base ch rnated propyl and 150- which has been treated with sulphur, for examplepropyl derivatives of phen-' a composition produced by the heating ofthe sulanthrene such as retene phur with a fixed oil such as lard oil orfish oil chlorinated iii-methyl anthraor to which sulphur or a sulphurcompound (e. g., cene di-phenyl di-sulphide) has been added so that achlorinated fl-methyl anthracertain amount of sulphur is present inactive or V cene loosely combined form. It has been found that achlorinated dimethyl anthralubricating composition containing from .50%to cenes 2.50% of sulphur in active or loosely combined chlorinatedpropyl and isoform is well suited for use as a lubricant accordpropylderivatives of aning to the present invention. These percentagesthracene are not to be construed, however, as limitations Cir but merelyas an indication of the proportion of sulphur in the form defined forgood results.

It has been found that for optimum results a certain relationship shouldbe maintained between the amount of. halogen or more specifically,-chlorine in the composition and the amount of sulphur, when thehalogenated compounds of the above class are added to asulphur-containing oil. It has been found that to a composition having alow content of sulphur in active or loosely com bined form, halogenatedcompounds should be added in correspondingly low concentrations for bestresults. When sulphur-treated oil is used in combination withhalogenated compounds, it should be noted that for sufiicientlydesirable results the major proportion of the ultimate composition neednot consist entirely of sulphurtreated oil but a suitable oil base, suchas a mineral "oil or vegetable oil may have added thereto minorquantities or proportions of either a sulphur-treated oil or elementalsulphur in solution and a halogenated compound.

As an example of the cooperative eiiect of halogenated organic compoundsand a sulphur compound of the type described, the table below shows theresults obtained when solutions in mineral oil of a sulphurized fixedoil alone, chlorinated diphenyl ether alone and the same concentrationsof both additions were tested on an Almen lubricant testing machine. Thefixed oil used was cotton seed oil and contained about 9.5% of sulphur.The chlorinated diphenyl ether contained a total of about chlorine. Theincrease in film strength of the oil caused by the compounds dissolvedin it is shown and is stated in terms of additional pounds of weightapplied to the loading arm of the machine required to cause breakdown ascompared with the mineral oil alone:

Percent of Percent of sulphurized chlorinated $223533; cottonseeddiphenyl load 011 ether For general use, a lubricating composition inaccordance with our invention may comprise a major proportion of asuitable oil base and minor proportions, i. e., less than of thepreviously named addition agents, More specifically, our inventioncontemplates incorporating with a suitableoil base a total of less than20% of addition agents of the previously enumerated types.

The optimum amount of the addition agents to be employed will dependlargely upon their physical characteristics and especially their efiecton the viscosity of the oil to which they are added. The particular usefor which the lubricant is intended is also a governing factor indetermining the amount of the compound to be added.

The limit of the amount of the addition agents state. Halogenated ringcompounds of this nature are therefore suitable as a base to which toadd the sulphur or sulphur-treated oil directly without any other oilbase such as mineral oil to form one type of lubricating compositioncontemplated by this invention.

It is to be understood that the so-called addition agents referred toherein shall be substantially oil-soluble or of such nature that theymay be included in the composition in the form of a stable colloidalsuspension, It should also be noted that certain of the addition agentscontemplated by this invention, while soluble in oil do not dissolvereadily therein. When such compounds are used they may be firstdissolved in materials such as, benzene, the chlorbenzenes, the higheralcohols such as amyl alcohol, acetone, petroleum naphtha, carbontetrachloride, tetrachloroethylene, aniline, tricresyl phosphate, etc..and the resulting solution then added to the lubricating composition:

The lubricating compositions herein described cating the engagingsurfaces of gears especially those of the worm and of the hypoid types,and

for lubricating any such surfaces when operating under heavy loads orwhenever extremely high unit pressures between such surfaces areencountered. These compositions. are also well adapted for lubricatingbearings and especially those of the heavy duty, slow speed type.

The lubricating compositions herein described are particularly usefulfor the purpose of lubricating gears and such bearings and wearingsurfaces generally as are not subjected to high tempera-. tures. Sincethe so-called addition agents employed in lubricating compositions madein accordance with the present invention are in general too active whensubjected to high tempera= tures, they are not particularly adapted foruse as lubricants in the crank cases of internal combustion engines.

This application is a continuation inpart of copending applicationSerial Number 649,734 filed December 31, 1932 and Serial Number 74%,690filed September 17, 1934.

Other modes of applying the principle of our invention may be employedinstead of the one explained, change being made as regards the materialsemployed in carrying out the process, provided the ingredient oringredients stated in any of the following claims or the equivalent ofsuch stated ingredient or ingredients be employed.

We'therefore particularly point out and distinctly claim as ourinvention:

l. A lubricating composition including as a principal lubricatingconstituent the combination of a halogenated organic ring compound andsulphur in solution in active form.

2. A lubricating composition including a principal lubricatingconstituent comprising the combination of a halogenated organic ringcompound and a sulphuratreated oil.

' 3. A lubricating composition including as a principal lubricatingconstituent the combination of ahalogenated organic ring compound and asulphur treated fixed oil. I

4. A lubricating composition including as a principal lubricatingconstituent the combination of a lubricating oil, a halogenated opganicring compound and sulphur in solution in active form.

5. A lubricating composition including as a (iii principal lubricatingconstituent the combination organic ring compound and sulphur insolution in active form.

6. A lubricating composition including as a principal lubricatingconstituent the combination of a fixed oil containing sulphur inchemical combination in active or loosely combined form, and a minorproportion of a halogenated organic ring compound.

7. A lubricating composition including as a principal lubricatingconstituent the combination 01' a fixed oil containing sulphur inchemical combination in active or loosely combined form, and a minorproportion of a chlorinated organic ring compound.

8. A lubricating composition including as a principal lubricatingconstituent the combination of a fixed oil containing sulphur inchemical combination in active or loosely combined form, and a minorproportion of a halogen bearing derivative of at least one compound ofthe class including benzene, naphthalene, and diphenyl.

9. A lubricating composition including a major proportion of mineral oiland minor proportions of both a halogenated organic ring compound andsulphur in solution in active form;

10. A lubricating composition including as a principal lubricatingconstituent the combination or a major proportion of mineral oil and insolution therein minor proportions of both a halogenated organiccompound and a separate organic compound containing sulphur in active orloosely combined form.

11. A lubricating composition including as a principal lubricatingconstituent the combination of a major proportion of mineral oil and inprincipal lubricating constituent the combination or a lubricating oil,a minor proportion of at least one compound of the class includinghalogen and oxygen bearing derivatives of henzene, naphthalene, anddiphenyl, and sulphur in solution in active form.

15. A lubricating composition including as a principal lubricatingconstituent the combination of a halogenated diphenyl ether and sulphurin solution in active form.

16. A lubricating composition comprising a major proportion of a sulphurtreated oil and a minor proportion of a stable, oil-soluble halogenatedorganic compound having a vapor pressure less than atmospheric at atemperature of 140 C.

, 17 A lubricating composition comprising a major proportion of asulphur treated oil and a minor proportion of a stable, oil-solublehalogenated ring compound having a vapor pressure less than atmosphericat a temperature of 140 C.

18. A lubricating composition comprising a ma jor proportion of asulphur treated oil and a minor proportion of a stable, oil-solublehalcgenated hydrocarbon having a vapor pressure less than atmospheric ata temperature of 140 C.

19. A lubricating composition comprising a major proportion of minerallubricating oil and minor proportions of both a halogenated organiccompound and an organic sulphur compound, said compounds being oilsoluble, having vapor pressure less atmospheric at a temperature of 140C. and present in amounts less than 20% based on the amount oflubricating oil.

20. A lubricating composition comprising a major proportion of minerallubricating oil to which have been added minor proportions of both achlorinated organic compound and sulphur in solution in active form,said chlorinated organic compound having a vapor pressure of less thanatmospheric at a temperature of 140 C.

- 21. A lubricating composition including as a minor proportion of astable, oil-soluble, halogenated hydrocarbon ring compound having avapor pressure less than atmospheric at a temperature of 140 C.

CARL F. PRU'I'ION. ALBERT K. SMITH.

